JP5395083B2 - Macrocyclic lactones as fragrances - Google Patents

Description

  The present invention relates to methyl-substituted double-unsaturated macrocyclic lactones containing 14 to 17 ring atoms. The invention further relates to odorants containing them and their use as fragrance compositions.

  Musk odorants are essential in perfumes to impart a functional character that distinguishes perfumes from those that are just floral bouquets or potpourri, which often make up more than 10% by weight of perfume formulations, This decisively affects the overall characteristics of the fragrance. Thus, there is a constant need for new and unique musk odorants that convey signatures to fragrances with specific harmonious side notes. These side notes should best harmonize with the floral heart of the composition, extending it to a fragrance foundation. Thus, a warm, sweet herbal, floral side note with aromatic character is most ideally suited. These signature masks must be more diffusive and strong in order to affect the entire composition.

  The macrocycle constitutes the only group of naturally occurring musks. Despite their relatively high price, their reliability and inherent characteristics make them highly valuable in perfumery. Most macrocyclic musks are saturated or contain only one double bond, while only three diunsaturated unsubstituted macrocyclic musks are known, ie powerful and extremely sexually stimulating (4E / Z, 8E) -Oxacyclohexadeca-4,8-dien-2-one isomer (4E / Z) mixture with the naturalic musk scent and sweet and warm sandalwood character (W. Tochtermann, P. Kraft, Synlett 1996, 1029), (3E / Z, 8E) -oxacyclohexadeca-3,8-diene- with musk scent with an unpleasant pear and mushroom scent 2-one isomer (3E / Z) mixture (G. Bunte, PhD Thesis, Christian-Albrechts-Universitat zu Kiel, 1996, 106-108) and fat-like, waxy, with a relatively weak musk scent ( 6Z, 10Z) -cyclopentadeca-6,10- Enone (C. Fehr, J. Galindo, O. Etter, W. Thommen, Angew. Chem. Int. Ed. 2002, 41, 4523) is.

  Surprisingly, we have a novel group of highly diffusive and powerful musk features that have the desired floral side note of warm, sweet herbal, aromatic character desired. The compound was found.

式中、ｎおよびｍは独立して１、２、３および４から選択され、ただし３≦ｎ＋ｍ≦６、例えばｎ＋ｍは４または５であり；
Ｃ−４とＣ−５との間の二重結合は（Ｅ）立体配置にあり、Ｃ−（７＋ｎ）とＣ−（８＋ｎ）との間の結合は（Ｚ）立体配置にある、
で表される化合物に言及する。 Accordingly, the present invention in one aspect is represented by formula (I)

In which n and m are independently selected from 1, 2, 3 and 4, provided that 3 ≦ n + m ≦ 6, for example n + m is 4 or 5;
The double bond between C-4 and C-5 is in the (E) configuration, and the bond between C- (7 + n) and C- (8 + n) is in the (Z) configuration.
Is referred to.

  The compounds of the present invention contain one chiral center and therefore exist as enantiomer racemates or enantiomerically enriched mixtures. However, it is preferred to use the compounds as a racemic mixture simply for economic reasons, since the cost of these odorants increases by resolving stereoisomers or using chiral starting materials. However, if it is desired to prepare individual stereoisomers, this can be done by stereoselective synthesis by methods known in the art such as preparative HPLC and GC on chiral stationary phases. Or can be achieved starting from available chiral raw materials such as optically active citronellol.

  A compound of the formula (I) in which m is 1 and n is 2 or 3, and a compound in which m is 2 and n is selected from 1, 2, 3 and 4 are specified according to the invention Represents a viewpoint.

  In a particular embodiment, the compound of formula (I) is (4E, 9Z) -13-methyloxacyclopentadeca-4,9-dien-2-one, (4E, 8Z) -12-methyloxa Cyclotetradeca-4,8-dien-2-one, (4E, 10Z) -13-methyloxa-cyclopentadeca-4,10-dien-2-one, (4E, 10Z) -14-methyloxacyclohexa Deca-4,10-dien-2-one, (4E, 11Z) -15-methyloxacycloheptadeca-4,11-dien-2-one and (4E, 9Z) -12-methyloxacyclo-tetradeca- Selected from 4,9-dien-2-one and mixtures thereof.

  Among the compounds of the present invention, (4E, 9Z) -13-methyloxacyclopentadeca-4,9-dien-2-one can be mentioned as a typical representative example. It exudes a scent of a sweet, aromatic, powdery musk with a strong feel that has a floral appearance in the direction of jasmine and slightly green. The scent of this compound is one of the closest prior art compounds: (4E / Z, 8E) -oxa with a natural, musk scent of an animal-like, powerful and extremely sexually stimulating animal with sweet warm sandalwood characteristics When compared with cyclohexadeca-4,8-dien-2-one, the latter has a sandalwood, woody property of (4E, 9Z) -13-methyloxacyclopentadeca-4,9-dien-2- It is completely lacking in ON, which is also as any animal-like implication.

  In contrast to (4E / Z, 8E) -oxacyclohexadeca-4,8-dien-2-one, (4E, 9Z) -13-methyloxacyclopentadeca-4,9-diene-2-one The on-musk features are floral-jasmine-like, and also sweet fragrance, and the green herb aspect is otherwise only common in the floral family. The floral and warm herbal aspect is also characteristic of the musk scent of (4E, 8Z) -12-methyloxacyclotetradec-4,8-dien-2-one, which also tends to be a metallic hot iron It is. This metal-like hot iron tendency also appears in other macrocyclic musks such as Habanolide (oxacyclohexadec-12 / 13-en-2-one), but never appears in the floral context. Thus, the compounds of formula (I) have an unexpected scent unlike those of their closest prior art analogs.

  The compounds of the present invention may be used alone, as a mixture thereof, or in combination with a base material. As used herein, “base materials” include a wide range of currently available natural and synthetic molecules such as ethereal oils and extracts, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones. In one or more components or excipients conventionally used in combination with odorants in fragrance compositions, macrocycles and heterocycles, and / or fragrance compositions, such as mixtures with carrier materials, and the like Other adjuvants commonly used in the field, such as diluents conventionally used in combination with odorants such as dipropylene glycol (DPG), isopropyl myristate (IPM) and triethyl citrate (TEC) As well as all alcohols (eg ethanol) selected It includes the odorant molecule of knowledge. The use of the compounds of formula (I) is not limited to any particular perfume type, nor to any particular olfactory direction, odorant or group of substances. Therefore, you may mix the compound represented with the said general formula with the following, for example.

Ethereal oils and extracts such as sea scented incense, costus root oil, oak moss absolute, geranium oil, jasmine absolute, patchouli oil, rose oil, sandalwood oil or ylang ylang oil;
Alcohols such as citronellol, Ebanol® (3-methyl-5- (2,2,3-trimethyl-3-cyclopenten-1-yl-4-penten-2-ol), eugenol, geraniol, super Super Muguet (6-ethyl-3-methyl-6-octen-1-ol), linalool, phenylethyl alcohol, Sandalore® (5- (2,2,3-trimethyl-3-cyclopentenyl) ) -3-methylpentan-2-ol), terpineol or Timberol® [1- (2,2,6-trimethylcyclohexyl) hexane-3-ol);

Aldehydes and ketones such as Azurone [7- (3-methylbutyl) -2H-1,5-benzodioxepin-3 (4H) -one], α-amylcinnamaldehyde, hydroxycitronellal Iso E Super [1- (2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl) ethanone] Isoraldeine, Hedione® [methyl (3-oxo-2-pentylcyclopentyl) acetate], maltol, methyl cedryl ketone, methyl ionone, Pomarose [(2E) -5,6,7 -Trimethylocta-2,5-dien-4-one] or vanillin;
Ethers and acetals, such as Ambrox® (3a, 6,6,9a-tetramethyldodecahydronaphtho [2,1-b] furan), geranyl methyl ether, rose oxide or spirambrene (2 , 2,3 ′, 7 ′, 7′-pentamethylspiro (1,3-dioxane-5,2′-norcaran));

Esters and lactones such as benzyl acetate, cedryl acetate, γ-decalactone, Helvetolide® (propanoic acid 2- [1- (3,3-dimethylcyclohexyl) ethoxy] -2-methylpropan-1-ol ), Serenolide (2- [1- (3,3-dimethylcyclohexyl) ethoxy] -2-methylpropan-1-olcyclopropanecarboxylate), [gamma] -undecalactone or vetibenyl acetate;
Macrocycles such as ambletlide, ethylene brushate or Exaltolide® (oxacyclohexadecan-2-one); and heterocycles such as isobutylquinoline.

  However, due to their unique musk characteristics, the compounds of the present invention are particularly well suited for use in combination with more prominent floral heart notes in both feminine and masculine fragrances.

  The compounds according to the invention can be used in all fields of a wide range of fragrance applications, for example fine and functional fragrances such as perfumes, household products, laundry products, body care products and cosmetics. The compounds can be used in amounts that vary widely depending on the particular application and the nature and amount of other fragrances. The proportions using the compounds of the invention can vary within a large range of values and depend on the nature of the intended use for the perfume, for example the nature of the co-ingredient.

  It also depends on the specific effect that the fragrance manufacturer is seeking. In general, however, when mixed with other products, such as laundry products, up to about 35% by weight of the compound of formula (I) or its mixture in perfume, for example about From 5% to about 30% and up to about 15% by weight can be used. However, these values are only given by way of example as experienced fragrance manufacturers can also achieve the effect or create new harmony with lower or higher concentrations.

  The compounds of the present invention can be used in a consumer product base simply by directly mixing the compound of formula (I), mixtures thereof, or by mixing the fragrance composition with the consumer product base. Or capturing them at a relatively early stage with capture materials such as polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof And / or chemically couple them to a substrate and adapt it to release the fragrance molecules of the present invention by applying external stimuli such as light, enzymes, etc., and then consumer products Can be mixed with the base.

  Accordingly, the present invention further provides a method for producing a fragrance-use product, comprising mixing a compound directly into a consumer product base, or a fragrance composition comprising a compound of formula (I) or a precursor thereof. Providing said method comprising mixing the compound of formula (I) as a fragrance component by mixing, which can then be mixed with a consumer product base using conventional techniques and methods To do. By adding an olfactory acceptable amount of a compound of the invention or mixture thereof, consumer product based scent notes are improved, enhanced and / or modified.

  “Precursors”, in particular, are cleaved in the product, for example after oxidation, enzymatic reaction, heating or treatment with base, thereby releasing the diunsaturated macrocyclic lactone of formula (I), It means an addition product at one or both of the double bonds of the compound represented by (I). Suitable reactions and corresponding substrates include all types of elimination formed by C═C double bonds, such as hydro-tosyloxy elimination, hydro-dialkyloxyammonio elimination, Hofmann degradation or Chugaev or Shapiro reactions . In particular, the ([7 + n] Z) configurational double bond can be advantageously formed from the corresponding α-halosulfone in a Ramberg-Backlund reaction.

  Accordingly, the present invention further provides a method for improving, enhancing and / or modifying a fragrance product, said method comprising adding to it an olfactory acceptable amount of a compound of formula (I) or a mixture thereof. I will provide a.

The present invention also includes:
A fragrance application comprising a) a compound of formula (I) or a mixture thereof; and b) a consumer product base.

  As used herein, “consumer product base” means a composition for use as a consumer product that fulfills certain behaviors such as cleaning, softening and caring. Examples of such products include fine perfumery such as perfumes and eau de toilettes; textile care, household and personal care products such as laundry care detergents, rinse conditioners, personal cleansing compositions, dishwasher detergents, Surface cleaning agents; laundry products such as softeners, bleaches, detergents; body care products such as shampoos, shower gels; air care products and cosmetics such as deodorants and vanishing cremes. This list of products is given by way of example and should not be considered limiting in any way.

式中、ｎおよびｍは独立して１、２、３および４から選択され、ただし３≦ｎ＋ｍ≦６、例えばｎ＋ｍは４または５である、
で表される化合物）のアルキンメタセシスにより、Schrockのカルビン触媒［Ｍｅ_３ＣＣ≡Ｗ（ＯｔＢｕ）_３］または他のアルキンメタセシス触媒の存在下で調製することができる。 The compound of formula (I) is converted to the corresponding alk-3-ene- [6 + n] -inic acid (3E) -3′-methylalk- [4 + m] ′-ynyl (ie, formula (II)

In which n and m are independently selected from 1, 2, 3 and 4, provided that 3 ≦ n + m ≦ 6, for example n + m is 4 or 5.
Can be prepared in the presence of Schrock's carbyne catalyst [Me ₃ CC≡W (OtBu) ₃ ] or other alkyne metathesis catalysts.

  Surprisingly, it has been found that alkyne metathesis does not compete with enyne metathesis in the case of the respective substrates as expected and thus constitutes another aspect of the invention. Alk-3-ene- [6 + n] -inic acid (3E) -3′-methylalk- [4 + m] -ynyl represented by the formula (II) is converted to alk-3-ene- [6 + n] inic acid. By a general esterification reaction with (3E) -3'-methylalk- [4 + m] '-inol, for example Steglich esterification using 4- (dimethylamino) -pyridine and N, N'-dicyclohexylcarbodiimide as catalyst. Can be conveniently prepared under conditions known to those skilled in the art.

  The alk-3-ene- [6 + n] -inic acid can be prepared according to the corresponding alkoxide, as described, for example, in N. Ragoussis et al. (In J. Chem. Soc., Perkin Trans. 1, 1998, 3529). -Obtained by [beta], [gamma] -selective Knoevenagel reaction in the presence of piperidinium acetate from [4 + n] '-inaldehydes, while preparing (3E) -3'-methylalk- [4 + m]'-inols To do so, several methods are known in the literature, including demethylation induced by nitrous acid of the isopropylidene group of citronellol to synthesize 3-methyloct-6-in-1-ol. (SL Abidi, Tetrahedron Lett. 1986, 27, 267) and Corey-Fuchs reaction of protected hydroxy aldehydes. The alk- [4 + n] -inaldehydes required to synthesize alk-3-ene- [6 + n] -in acids are converted to 2-methyl substituted cycloalk-2-enones after Weitz-Scheffer epoxidation. Prepared by Eschenmoser-Ohloff reaction or by methylation of terminal alkynols by the procedure of Herndon et al. (J. Yan, J. Zhu, JJ Matasi, JW Herndon, J. Org. Chem. 1990, 55, 786) be able to.

The invention will now be further described with reference to the following non-limiting examples. It is understood that these examples are for illustrative purposes only, and that changes and modifications can be made by those skilled in the art. NMR data is shown relative to an internal SiMe ₄ standard.

Example 1:. (4E, 9Z) -13- methyl-oxacyclopenta deca-4,9-dien-2-one oct-6 Inaru, J Yan, J. Zhu, JJ Matasi, JW Herndon, J. Org Synthesized with additional THP protection during the methylation step according to the synthesis scheme of Chem. 1990, 55, 786. Commercially available hexa-5-in-1-ol (15.2 g, 155 mmol) was protected (DHP, PTSA, CH ₂ Cl ₂ , 0 ° C. → room temperature, 5 hours) and then methylated (1. 6M BuLi, MeI, THF, −78 ° C. → room temperature, 12 hours). Cleavage of THP ether (PPTS, MeOH, room temperature, 12 hours) gave hepta-5-in-1-ol (10.6 g, 61%), which was mesylated (MsCl, Et ₃ N, Et ₂ O, 0 ° C. → room temperature, 12 hours) followed by cyanation (KCN, DMF, reflux, 3.5 hours) to provide octa-6-nitrile (7.90 g, 69%). Reduction of the nitrile (DIBAL-H, THF, 0 ° C. → room temperature, 12 hours) gave octa-6-inal (6.70 g, 83%).

At room temperature, a freshly prepared piperidinium acetate solution was prepared by mixing piperidine (110 μL, 1.10 mmol) and acetic acid (65.0 μL, 1.10 mmol) in dimethylsulfoxide (5.00 mL). 6-Inal (6.70 g, 54.0 mmol) and malonic acid (11.2 g, 108 mmol) were poured into a stirred solution of dimethyl sulfoxide (200 mL). After the reaction mixture was refluxed for 4 hours, water (50 mL) and ether (100 mL) were added at room temperature and the layers were separated. The aqueous layer was extracted with ether (3 × 100 mL) and the combined organic extracts were washed with water (100 mL), dried (Na ₂ SO ₄ ) and concentrated under reduced pressure. The crude material (GC, Δ ³ : Δ ² = 70: 30) was purified by chromatography on silica gel [200 g; pentane-Et ₂ O (4: 1); R _f = 0.24, pentane-Et _2. O (5: 1)] and then Kugelrohr distillation at 160 ° C./13 mbar to give (3E) -dec-3-ene-8-inonic acid (3.79 g, 42%) as a colorless crystalline solid (melting point 40-43 ° C).

At room temperature, 4- (dimethylamino) pyridine (122 mg, 0.999 mmol) was added to (3E) -dec-3-ene-8-inonic acid (1.66 g, 9.99 mmol) and 3-methyloct-6- In-1-ol (1.40 g, 9.99 mmol) was added to a stirred solution of ether (30 mL). 3-Methyloct-6-in-1-ol (1.80 g, 26%) was added to citronellol (7.81 g, 50.0 mmol) and sodium nitrite (93. g) in acetic acid / water (5: 2, 210 mL). 2 g, 135 mmol) from SL Abidi, Tetrahedron Lett. 1986, 27, 267. At 0 ° C., N, N′-dicyclohexylcarbodiimide (2.27 g, 11.0 mmol) was added and the reaction mixture was stirred at this temperature for 10 minutes, which produced a colorless precipitate. The insoluble material was filtered off with suction in a sintered funnel and the filtrate was concentrated under reduced pressure. Chromatography of the resulting residue on silica gel [50 g; pentane-Et ₂ O (20: 1); R _f = 0.50, in pentane-Et ₂ O (10: 1)] gave deca-3 -En-8-inoic acid (3E) -3'-methylocta-6'-ynyl (1.34 g, 47%) was obtained as a colorless liquid.

Deca-3-ene-8-inonic acid (3E) -3′-methylocta-6′-ynyl (435 mg, 1.51 mmol) dissolved in anhydrous chlorobenzene (80 mL) was degassed with argon for 15 minutes, Then Schrock's Calvin catalyst (Me ₃ CC≡W (OtBu) ₃ , 71.3 mg, 0.151 mmol) was added. With a slow flow of argon, the resulting mixture was refluxed for 24 hours and then allowed to cool to room temperature. The solvent was removed under reduced pressure and the residue obtained was chromatographed on silica gel [50 g; pentane-Et ₂ O (50: 1); R _f = 0.44, pentane-Et ₂ O (5: 1). Medium] afforded (4E) -13-methyloxacyclo-pentadec-4-en-9-in-2-one (150 mg, 42%) as a colorless liquid.

Quinoline (4.86 μL, 0.0411 mmol) and 10% Pd / BaSO ₄ (0.88 mg, 0.00824 mmol) were added to (4E) -13-methyloxacyclopentadec-4-ene-9-in-2- On (48.2 mg, 0.206 mmol) was added to a stirred solution in ethanol (2.0 mL). The reaction flask was flushed with argon followed by hydrogen and the reaction mixture was stirred at room temperature and ambient pressure under a hydrogen atmosphere. After 3.5 hours, GC monitoring showed complete conversion, at which time the catalyst was filtered off through a pad of celite and washed with ethanol. The solvent was removed under reduced pressure and the residue obtained was chromatographed on silica gel [20 g; pentane-Et ₂ O (10: 1); R _f = 0.78, pentane-Et ₂ O (5: 1). Medium] gave (4E, 9Z) -13-methyloxacyclopentadeca-4,9-dien-2-one (44.8 mg, 92%) as a colorless odorous liquid.

香りの記載：フローラルの様相を有し、ジャスミンおよびわずかにグリーンの性状の方向にある強度であり良好な感じの甘い芳香性のパウダリーなムスクの香り。

Scent description: A sweet, aromatic, powdery musk scent that is floral and has a strong feel in the direction of jasmine and a slight green character.

Example 2: (4E, 8Z) -12-methyloxacyclotetradec- 4,8-dien-2-one At room temperature, 2N aqueous sodium hydroxide solution (7.00 mL, 14.0 mmol), followed by 30% excess Aqueous hydrogen oxide (11.0 mL, 112 mmol) was added to a stirred solution of commercially available 2-methylcyclohex-2-enone (2.20 g, 20.0 mmol) in methanol (250 mL) and the The red color generated by the solution disappeared within 10 minutes. After stirring at room temperature for 24 hours, the reaction mixture was diluted with water (200 mL) and extracted with dichloromethane (3 × 150 mL). The combined organic extract was washed with water (200 mL) and dried over sodium sulfate. The solvent was removed under reduced pressure and the resulting residue was purified by chromatography on silica gel [40 g; pentane-Et ₂ O (9: 1); R _f = 0.29] to give 1-methyl-7. -Oxabicyclo [4.1.0] heptan-2-one (1.18 g, 47%) was obtained as a colorless liquid.

At −10 ° C., p-toluenesulfonylhydrazine (6.14 g, 33.0 mmol) was replaced with 1-methyl-7-oxabicyclo [4.1.0] heptan-2-one (3.78 g, 30.0 mmol). ) Was added in portions to a stirred solution in acetic acid / dichloromethane (1: 1, 80 mL). The reaction mixture was allowed to warm slowly by not supplying fresh cooling medium and at 10 ° C. GC monitoring showed complete conversion. Crushed ice (20 g) was added and the layers were separated. The aqueous layer was extracted with dichloromethane (2 × 50 mL) and the combined organic solution was neutralized with ice-cold saturated aqueous sodium bicarbonate. After drying over sodium sulfate and removal of the solvent under reduced pressure, chromatographic separation of the residue obtained on silica gel [50 g; pentane-Et ₂ O-Et ₃ N (3: 1: 0.01); R _f = 0.48 in pentane-Et ₂ O (5: 1)] gave hepta-5-inal (1.74 g, 53%) as a colorless liquid.

A freshly prepared piperidinium acetate solution was prepared by mixing piperidine (35.0 μL, 0.354 mmol) and acetic acid (19.0 μL, 0.332 mmol) in dimethyl sulfoxide (1.00 mL) at room temperature. Hept-5-ynal (1.50 g, 13.6 mmol) and malonic acid (2.83 g, 27.2 mmol) were poured into a stirred solution of dimethyl sulfoxide (50 mL). After refluxing the reaction mixture for 4 hours, water (10 mL) and ether (20 mL) were added at room temperature and the layers were separated. The aqueous layer was extracted with ether (3 × 25 mL) and the combined organic extracts were washed with water (25 mL), dried (Na ₂ SO ₄ ) and concentrated under reduced pressure. Kugelrohr distillation at 149 ° C./14 mbar gave (3E) -non-3-ene-7-inoic acid (902 mg, 44%) as colorless crystals (melting point 43-45 ° C.).

At room temperature, 4- (dimethylamino) pyridine (68.4 mg, 0.559 mmol) was added to (3E) -non-3-ene-7-inonic acid (850 mg, 5.59 mmol) and 3-methyloct-6- In-1-ol (790 mg, 5.59 mmol) was added to a stirred solution in ether (20 mL). 3-Methyloct-6-in-1-ol (1.80 g, 26%) was added to citronellol (5: 2, 210 mL) in acetic acid / water (5: 2, 210 mL) according to the procedure of SL Abidi, Tetrahedron Lett. 1986, 27, 267. Prepared from 7.81 g, 50.0 mmol) and sodium nitrite (93.2 g, 135 mmol). At 0 ° C., N, N′-dicyclohexylcarbodiimide (1.27 g, 6.14 mmol) was added and the reaction mixture was stirred at this temperature for 5 minutes, at which time a colorless precipitate formed. The insoluble material was filtered off with suction in a sintered funnel and the filtrate was concentrated under reduced pressure. Chromatography of the resulting residue on silica gel [50 g; pentane-Et ₂ O (20: 1); R _f = 0.65, in pentane-Et ₂ O (5: 1)] gives non-3 -En-7-inoic acid (3E) -3'-methylocta-6'-ynyl (470 mg, 31%) was obtained as a colorless liquid.

Nona-3-ene-7-inonic acid (3E) -3′-methylocta-6′-ynyl (350 mg, 1.28 mmol) dissolved in anhydrous chlorobenzene (120 mL) was degassed with argon for 15 minutes, Then Schrock's Calvin catalyst (Me ₃ CC≡W (OtBu) ₃ , 60.5 mg, 0.128 mmol) was added. With a slow flow of argon, the resulting mixture was refluxed for 24 hours and then allowed to cool to room temperature. The solvent was removed under reduced pressure and the residue obtained was chromatographed on silica gel [50 g; pentane-Et ₂ O (1: 1); R _f = 0.55, pentane-Et ₂ O (5: 1). Medium] gave (4E) -12-methyloxacyclotetradec-4-en-8-in-2-one (220 mg, 78%) as a colorless liquid.

Quinoline (27.5 μL, 0.232 mmol) and 10% Pd / BaSO ₄ (4.90 mg, 0.0461 mmol) were added to (4E) -12-methyloxacyclotetradec-4-ene-8-in-2- On (256 mg, 1.16 mmol) was added to a stirred solution in ethanol (20 mL). The reaction flask was flushed with argon followed by hydrogen and the reaction mixture was stirred at room temperature and ambient pressure under a hydrogen atmosphere. After 5 hours, GC monitoring showed complete conversion, at which time the catalyst was filtered off through a pad of celite and washed with ethanol. The solvent was removed under reduced pressure and the residue obtained was chromatographed on silica gel [30 g; pentane-Et ₂ O (20: 1); R _f = 0.60, pentane-Et ₂ O (5: 1). Medium] gave (4E, 8Z) -12-methyloxacyclotetradeca-4,8-dien-2-one (223 mg, 86%) as a colorless odorous liquid.

香りの記載：ハーブおよびフローラルの様相を有する強力な暖かい、金属様の、パウダリーなムスクの香り、ならびに強力なホットアイロンの傾向。

Scent description: Strong warm, metallic, powdery musk scent with herbal and floral aspects, and strong hot ironing tendency.

Example 3 Other Compounds The following compounds can also be prepared according to the general procedure described by Examples 1 and 2:
(4E, 8Z) -13-methyloxacyclopentadeca-4,8-dien-2-one,
(4E, 8Z) -14-methyloxacyclohexadeca-4,8-dien-2-one,
(4E, 9Z) -12-methyloxacyclotetradeca-4,9-dien-2-one,
(4E, 9Z) -14-methyloxacyclohexadeca-4,9-dien-2-one,
(4E, 9Z) -15-methyloxacycloheptadeca-4,9-dien-2-one,
(4E, 10Z) -13-methyloxacyclo-pentadeca-4,10-dien-2-one,
(4E, 10Z) -14-methyloxacyclohexadeca-4,10-dien-2-one,
(4E, 10Z) -15-methyloxacycloheptadeca-4,10-dien-2-one,
(4E, 11Z) -14-methyloxacyclohexa-deca-4,11-dien-2-one and (4E, 11Z) -15-methyloxacycloheptadeca-4,11-dien-2-one.

Example 4: Women's fine fragrance “Jasmine-white Amber and Green Apple”

  At 10%, (4E, 9Z) -13-methyloxacyclopentadeca-4,9-dien-2-one (Example 1) is characterized by this floral composition around the harmony of the central Jasminium sambac Conveys a classic floral signature mosque note, which is the foundation of a soft, warm, good-feeling sweet aromatic powdery musk with the characteristics of a slightly green herb that incorporates cyclal C, the top-note green apple Extend the theme of jasmine. (4E, 9Z) -13-methyloxacyclo-pentadeca-4,9-dien-2-one is well combined to enhance the properties of the powdery nitromusk of the macrocyclic ketone COSMONE®, and further to woody Increase the musk-like features of the musk-like substance CASHMERAN®, thereby creating a round rich signature musk harmony in dry-down. Along with spirambrene and amber ketal, the floral, jasmine-like musk note of (4E, 9Z) -13-methyloxacyclopentadeca-4,9-dien-2-one is a unique “white amber” theme, ie unique A white-floral musk-like Ambergris note, which to date, without a floral musk such as (4E, 9Z) -13-methyloxacyclopentadec-4,9-dien-2-one Could not be realized in a lush and active way.

Claims (5)

Formula (I)

In which n and m are independently selected from 1, 2, 3 and 4, provided that 3 ≦ n + m ≦ 6;
The double bond between C-4 and C-5 is in the (E) configuration, and the bond between C- (7 + n) and C- (8 + n) is in the (Z) configuration.
A compound represented by   (4E, 8Z) -12-methyloxacyclotetradeca-4,8-dien-2-one, (4E, 8Z) -13-methyloxacyclopentadeca-4,8-dien-2-one, (4E , 8Z) -14-methyloxacyclohexadeca-4,8-dien-2-one, (4E, 9Z) -12-methyloxacyclotetradeca-4,9-dien-2-one, (4E, 9Z ) -13-methyloxacyclopentadeca-4,9-dien-2-one, (4E, 9Z) -14-methyloxacyclohexadeca-4,9-dien-2-one, (4E, 9Z)- 15-methyloxacycloheptadeca-4,9-dien-2-one, (4E, 10Z) -13-methyloxacyclo-pentadeca-4,10-dien-2-one, (4E, 10Z) -14 Methyloxa Clohexadeca-4,10-dien-2-one, (4E, 10Z) -15-methyloxacycloheptadeca-4,10-dien-2-one, (4E, 11Z) -14-methyloxacyclohexa-deca 2. A compound according to claim 1 selected from -4,11-dien-2-one and (4E, 11Z) -15-methyloxacycloheptadeca-4,11-dien-2-one. Formula (I)

In which n and m are independently selected from 1, 2, 3 and 4, provided that 3 ≦ n + m ≦ 6;
The double bond between C-4 and C-5 is in the (E) configuration, and the bond between C- (7 + n) and C- (8 + n) is in the (Z) configuration.
Or a mixture thereof as a fragrance. A fragrance comprising a compound of formula (I) as defined in claim 1 or a mixture thereof and a consumer product base selected from the group consisting of fine fragrances, household products, textile care products, personal care products and cosmetics. Products used. Formula (I)

In which n and m are independently selected from 1, 2, 3 and 4, provided that 3 ≦ n + m ≦ 6;
The double bond between C-4 and C-5 is in the (E) configuration, and the bond between C- (7 + n) and C- (8 + n) is in the (Z) configuration.
A method for preparing a compound represented by
Formula (II)

Where n and m are as defined above .
In comprising an alkyne metathesis of a compound represented by said method.